CN111655372B

CN111655372B - Catalysts containing furans and their use in hydrotreating and/or hydrocracking processes

Info

Publication number: CN111655372B
Application number: CN201880075644.3A
Authority: CN
Inventors: P-L.卡雷特; D.德尔克鲁瓦
Original assignee: IFP Energies Nouvelles IFPEN
Current assignee: IFP Energies Nouvelles IFPEN
Priority date: 2017-11-22
Filing date: 2018-11-12
Publication date: 2023-07-25
Anticipated expiration: 2038-11-12
Also published as: BR112020006961A2; CN111655372A; RU2768503C2; FR3073753B1; RU2020119167A; FR3073753A1; US20200391191A1; JP7291699B2; EP3713669A1; US11027262B2; RU2020119167A3; JP2021504102A; WO2019101564A1

Abstract

The present invention relates to a catalyst comprising a support based on alumina, silica or silica-alumina, at least one element of group VIII, at least one element of group VIB and furans, to a process for the production of said catalyst, and to the use of said catalyst in a hydrotreating and/or hydrocracking process.

Description

Catalysts containing furans and their use in hydrotreating and/or hydrocracking processes

The present invention relates to catalysts impregnated with additives using furans, to a process for their preparation and to their use in the field of hydrotreatment and/or hydrocracking.

In general, catalysts for the hydrotreatment of hydrocarbon-based fractions have the function of removing sulfur-or nitrogen-based compounds contained in said fractions, for example in order to bring petroleum products to the desired specifications (sulfur content, aromatic content, etc.) for a given application (motor vehicle fuel, gasoline or gas oil, household fuel oil, jet fuel). It may also be concerned with pre-treating this feedstock to remove impurities therefrom or to hydrogenate it before subjecting it to various conversion processes (e.g. reforming, vacuum distillate hydrocracking, catalytic cracking, or atmospheric or vacuum residuum conversion processes) to alter its physicochemical properties. The composition and use of hydrotreating catalysts is described particularly well in articles taken from publications Catalysis Science and Technology, volume 11, 1996, springer-Verlag, B.S. Clausen, H.T. Tops, bush and F.E. Massoth.

Conventional hydrotreating catalysts typically comprise an oxide support and an active phase based on the oxide forms of the group VIB and group VIII metals and phosphorus. The preparation of these catalysts generally comprises the following steps: the support is impregnated with metal and phosphorus, and then dried and calcined to enable the active phase to be contained in its oxide form. These catalysts are typically subjected to sulfiding to form the active material prior to use in hydrotreating and/or hydrocracking reactions.

Those skilled in the art have suggested adding organic compounds to hydroprocessing catalysts to improve their activity, especially for catalysts prepared by impregnation followed by drying without subsequent calcination. These catalysts are often referred to as "additive impregnated dried catalysts".

Many documents describe the use of various organic compounds as additives, for example nitrogen-based organic compounds and/or oxygen-based organic compounds.

One class of compounds known today from the literature involves chelation of nitrogen-based compounds with, for example, ethylenediamine tetraacetic acid (EDTA), ethylenediamine, diethylenetriamine, or nitrilotriacetic acid (NTA) (EP 0 181 035, EP 1 043 069 and US 6 540 908).

Among the families of oxygen-based organic compounds, the use of optionally etherified mono-, di-or polyols is described in WO 96/41848, WO 01/76741, US 4 012 340, US 3 954 673, EP 601 722 and WO 2005/035691.

Some patents also claim the use of carboxylic acids (EP 1 402 948, EP 0482 817). In particular in EP 0482 817, citric acid and tartaric acid, butyric acid, hydroxycaproic acid, malic acid, gluconic acid, glyceric acid, glycolic acid and hydroxybutyric acid have been described. The specificity is that drying, which must be carried out at temperatures below 200 ℃.

The prior art mentions that the frequency of additives comprising ester functions is relatively low (EP 1 046 424, WO 2006/077326).

US 2014/0353213 describes the use of lactams, cyclic esters (of the lactone type) or cyclic ethers (of the oxacycloalkane type).

Regardless of the compound selected, the modification caused may not always sufficiently increase the performance of the catalyst to meet the specifications of the fuel with respect to sulfur and/or nitrogen content. Furthermore, because the implementation of the methods is overly complex, it is often very difficult to industrially deploy them.

Thus, catalyst manufacturers seem to have had to find novel hydrotreating and/or hydrocracking catalysts with improved performance.

Disclosure of Invention

The invention relates to a catalyst comprising a support based on alumina or silica-alumina, at least one element of group VIII, at least one element of group VIB and a furanic compound.

The applicant has in fact found that the use of furans as organic additives in catalysts containing at least one element of group VIII and at least one element of group VIB makes it possible to obtain hydrotreating and/or hydrocracking catalysts exhibiting improved catalytic performances.

In particular, the catalysts according to the invention show increased activity relative to known catalysts which are not impregnated with additives and to known dried catalysts impregnated with additives. Typically, by increasing the activity, the temperature required to achieve the desired sulfur or nitrogen content (e.g., 10ppm sulfur in the case of gas oil feedstock in ULSD or ultra low sulfur diesel modes) can be reduced. Similarly, stability is increased because the cycle time is extended by lowering the required temperature.

According to one variant, the furans have the formula (I)

Wherein the radicals R1, R2, R3 and R4 are each chosen from hydrogen atoms, groups containing from 1 to 20 carbon atoms based on linear or branched or cyclic hydrocarbons, chosen from the following functional groups: aldehyde-C (O) H, ketone-C (O) R ₅ Carboxylic acid-COOH, ester-COOR ₆ hydroxymethyl-CH ₂ OH, alkoxymethyl-CH ₂ OR ₇ halomethyl-CH ₂ X wherein x=cl, br OR I, acyl halide-COX wherein x=cl, br OR I, alcohol-OH, ether OR ₈ mercaptomethyl-CH ₂ SH, (alkylthio) methyl (alkylsulfanyl) methyl) -CH ₂ SR ₉ thioester-COSR ₁₀ Wherein R is ₅ To R ₁₀ Represents a group having from 1 to 20 carbon atoms based on a linear or branched or cyclic hydrocarbon, each of said groups R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 may further comprise heteroatoms, halogens and/or at least one functional group selected from: hydroxyl functionality, aldehyde functionality, ketone functionality, carboxyl functionality, alkanoate functionality, thiol functionality, alkylthio functionality, thioalkanoate functionality, and amine functionality.

According to this variant, the radicals R3 and R4 each advantageously represent a hydrogen atom.

According to one variant, the furans are selected from the group consisting of 2-methylfuran, 2, 5-dimethylfuran, furfuryl alcohol, 1- (2-furyl) ethanol, 2, 5-bis (hydroxymethyl) furan, 5- (hydroxymethyl) furfural, 5-hydroxymethyl-2-furoic acid, 2-methoxyfuran, 2-furaldehyde, 5-methyl-2-furaldehyde, 5- (ethoxymethyl) furan-2-formaldehyde, 5-acetoxymethyl-2-furaldehyde, 5-chloromethylfurfural, 2, 5-diformylfuran, 2-acetylfuran, 2-acetyl-5-methylfuran, furoic acid, 5-ethylfuroic acid, 5-formyl-2-furoic acid, 2, 5-furandicarboxylic acid, dimethyl 2, 5-furandicarboxylic acid, methyl 2-furoate, methyl 5-methyl-2-furoate, furylacetate, furyl propionate, furylthio, 2- [ (methylthio) methyl ] furan, furothioformate, furoate, thiofuroate, 2-thiofurfuroate, 3- (methylfurfuryl) furoate, and ethyl thiofurfuroate.

According to another variant, the furans are polyfurans (polyfurans) having formula (II):

wherein Z is selected from oxygen atoms, sulfur atoms, groups based on linear or branched or cyclic hydrocarbons, said groups comprising from 1 to 20 carbon atoms, and which may further comprise heteroatoms, halogens and/or at least one functional group selected from: hydroxyl functionality, aldehyde functionality, ketone functionality, carboxyl functionality, alkanoate functionality, thiol functionality, alkylthio functionality, thioalkanoate functionality, and amine functionality,

and wherein the radicals R1 and R2 are each selected from a hydrogen atom, a group containing 1 to 20 carbon atoms based on a linear or branched or cyclic hydrocarbon, a functional group selected from: aldehyde-C (O) H, ketone-C (O) R ₅ Carboxylic acid-COOH, ester-COOR ₆ hydroxymethyl-CH ₂ OH, alkoxymethyl-CH ₂ OR ₇ halomethyl-CH ₂ X wherein x=cl, br OR I, acyl halide-COX wherein x=cl, br OR I, alcohol-OH, ether OR ₈ mercaptomethyl-CH ₂ SH, (alkylthio) methyl-CH ₂ SR ₉ thioester-COSR ₁₀ Wherein R is ₅ To R ₁₀ Represents a group having from 1 to 20 carbon atoms based on a linear or branched or cyclic hydrocarbon, said groups R1, R2, R5, R6, R7, R8, R9 and R10 each may also comprise heteroatoms, halogens and/or at least one functional group chosen from: hydroxy functional groups, aldehyde functional groups, Ketone functional groups, carboxyl functional groups, alkanoate functional groups, thiol functional groups, alkylthio functional groups, thioalkanoate functional groups, and amine functional groups.

According to this variant, the furans are selected from the group consisting of bis (5-formylfurfuryl) ether, 2' - (thiodimethylene) difuran and 5, 5-bis (5-methyl-2-furyl) -2-pentanone.

According to a variant, the content of the group VIB element expressed as a group VIB metal oxide is from 5% to 40% by weight relative to the total weight of the catalyst, and the content of the group VIII element expressed as a group VIII metal oxide is from 1% to 10% by weight relative to the total weight of the catalyst.

According to a variant, the molar ratio of the group VIII element to the group VIB element in the catalyst is between 0.1 and 0.8.

According to a variant, the catalyst also contains phosphorus as P ₂ O ₅ The phosphorus content represented is from 0.1% to 20% by weight relative to the total weight of the catalyst, and the molar ratio of phosphorus to group VIB elements in the catalyst is greater than or equal to 0.05.

According to a variant, the furans are present in an amount of 1% to 45% by weight relative to the total weight of the catalyst.

According to a variant, the catalyst also contains organic compounds other than furans, which contain oxygen and/or nitrogen and/or sulfur.

According to this variant, the organic compound is selected from compounds comprising one or more chemical functional groups selected from: carboxyl, alcohol, thiol, thioether, sulfone, sulfoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea, and amide functionalities.

According to this variant, the organic compounds other than furans are selected from gamma valerolactone, 2-acetyl butyrolactone, triethylene glycol, diethylene glycol, ethylene glycol, ethylenediamine tetraacetic acid (EDTA), maleic acid, malonic acid, citric acid, gamma ketovaleric acid, dimethylformamide, N-methylpyrrolidone, propylene carbonate, 2-methoxyethyl 3-oxobutyrate, 2-methacryloyloxyethyl 3-oxobutyrate, N-bis (hydroxyethyl) glycine (bicine), tris (hydroxymethyl) methylglycine (tricine) or lactam.

According to a variant, the catalyst is at least partially sulfided.

The invention also relates to a method for preparing a catalyst according to the invention as described in the claims.

The invention also relates to the use of the catalyst according to the invention in a process for the hydrotreatment and/or hydrocracking of a hydrocarbon-based fraction.

Hereinafter, the family of chemical elements is given according to CAS taxonomy (CRC Handbook of Chemistry and Physics, published by CRC Press, D.R. hide, 81 st edition, 2000-2001). For example, group VIII according to CAS classification corresponds to the metals of columns 8, 9 and 10 according to the new IUPAC classification.

The term "hydrotreating" refers to reactions including, inter alia, hydrodesulfurization (HDS), hydrodenitrogenation (HDN), and hydrogenation of aromatics (HOA).

Detailed description of the invention

Catalyst

The catalyst according to the invention is a catalyst impregnated with an additive using furans. More particularly, the catalyst according to the invention comprises a support based on alumina or silica-alumina, at least one element of group VIII, at least one element of group VIB, and furans.

The term "furans" means any compound containing at least one aromatic ring consisting of four carbon atoms and one oxygen atom.

The catalyst according to the invention may be a fresh catalyst, i.e. a catalyst which has not been used previously as a catalyst in catalytic units, in particular in hydrotreating and/or hydrocracking.

The catalyst according to the invention may also be a reconstituted catalyst (rejuvenated catalyst). The term "reconstituted catalyst" means a catalyst which has been used as a catalyst in a catalytic unit and in particular in hydrotreating and/or hydrocracking, and which has undergone at least one step of partial or complete removal of coke, for example by calcination (regeneration). The regenerated catalyst is then subjected to additive impregnation with at least one furanic compound to obtain a reconstituted catalyst. The reconstituted catalyst may contain one or more other organic additives, which may be added before, after, or simultaneously with the furans.

The hydrogenation function of the catalyst, also called the active phase, is provided by at least one group VIB element and at least one group VIII element.

Preferred group VIB elements are molybdenum and tungsten. Preferred group VIII elements are non-noble metal elements, and in particular cobalt and nickel. Advantageously, the hydrogenation function is selected from the group consisting of elemental cobalt-molybdenum, nickel-tungsten, or nickel-cobalt-molybdenum, or a combination of nickel-molybdenum-tungsten.

Where significant hydrodesulfurization or hydrodenitrogenation activity or significant para-aromatic hydrogenation activity is desired, the hydrogenation function is advantageously provided by a combination of nickel and molybdenum; a combination of nickel and tungsten in the presence of molybdenum may also be advantageous. In the case of a feedstock such as a vacuum distillate or a heavier distillate, a combination of cobalt-nickel-molybdenum types may be advantageously used.

The total content of elements of groups VIB and VIII, expressed as oxides, is advantageously greater than 6% by weight relative to the total weight of the catalyst.

The content of the group VIB element expressed as the group VIB metal oxide is 5 wt% to 40 wt%, preferably 8 wt% to 35 wt%, and more preferably 10 wt% to 30 wt% with respect to the total weight of the catalyst.

The content of the group VIII element expressed as the group VIII metal oxide is 1 to 10 wt%, preferably 1.5 to 9 wt%, and more preferably 2 to 8 wt%, with respect to the total weight of the catalyst.

The molar ratio of group VIII element to group VIB element in the catalyst is preferably 0.1 to 0.8, preferably 0.15 to 0.6, and even more preferably 0.2 to 0.5.

The catalyst according to the invention also advantageously comprises phosphorus as dopant. The dopant is an added element that does not itself have catalytic properties, but increases the catalytic activity of the active phase.

As P in the catalyst ₂ O ₅ The phosphorus content expressed is from 0.1% to 20% by weight, preferably as P, relative to the total weight of the catalyst ₂ O ₅ Expressed from 0.2 to 15% by weight, and very preferably as P ₂ O ₅ Expressed as 0.3 to 11% by weight.

The molar ratio of phosphorus to group VIB element in the catalyst is greater than or equal to 0.05, preferably greater than or equal to 0.07, preferably from 0.08 to 1, preferably from 0.01 to 0.9, and very preferably from 0.15 to 0.8.

The catalyst according to the invention may also advantageously contain, with or without phosphorus, at least one dopant selected from boron, fluorine and mixtures of boron and fluorine.

When the catalyst contains boron, the boron content expressed as boron oxide is preferably 0.1 to 10% by weight, preferably 0.2 to 7% by weight, and very preferably 0.2 to 5% by weight relative to the total weight of the catalyst.

When the catalyst contains fluorine, the fluorine content expressed as fluorine is preferably 0.1 to 10% by weight, preferably 0.2 to 7% by weight, and very preferably 0.2 to 5% by weight relative to the total weight of the catalyst.

When the catalyst contains boron and fluorine, the total content of boron and fluorine expressed as boron oxide and fluorine is preferably 0.1 to 10% by weight, preferably 0.2 to 7% by weight, and very preferably 0.2 to 5% by weight relative to the total weight of the catalyst.

The catalyst according to the invention comprises a support based on alumina or silica-alumina.

When the support of the catalyst is based on alumina, it contains more than 50% by weight of alumina relative to the total weight of the support, and generally it contains only alumina or silica-alumina as defined below.

Preferably, the support comprises alumina, and preferably extruded alumina. Preferably, the alumina is gamma alumina.

The alumina support advantageously has a length of 0.1 to 1.5cm ³ .g ^-1 Preferably 0.4 to 1.1cm ³ .g ^-1 Is defined by the total pore volume of the polymer. Such as Rouquerol F.; rouquerol J.; book "Adsorption by Powders" by Singh K. The invention also relates to a method of preparing such a composition&The total pore volume is measured by mercury porosimetry at a wetting angle of 140℃according to standard ASTM D4284, for example, by Micromeritics ™ brand Autopore III ™ machine, described in principles, methodology and applications ", academic Press, 1999.

The specific surface area of the alumina support is advantageously from 5 to 400m ² .g ^-1 Preferably 10 to 350m ² .g ^-1 More preferably 40 to 350m ² .g ^-1 . The specific surface area is determined in the present invention by the BET method according to standard ASTM D3663, which is described in the same book cited above.

In another preferred case, the support of the catalyst is silica-alumina containing at least 50% by weight of alumina relative to the total weight of the support. The silica content in the support is at most 50% by weight, generally less than or equal to 45% by weight, preferably less than or equal to 40% by weight, relative to the total weight of the support.

The source of silicon is well known to those skilled in the art. Examples which may be mentioned include silicic acid, silicon dioxide in powder form or in colloidal form (silica sol), and tetraethyl orthosilicate Si (OEt) ₄ 。

When the support of the catalyst is based on silica, it contains more than 50% by weight of silica relative to the total weight of the support, and it generally contains only silica.

According to a particularly preferred variant, the support consists of alumina, silica or silica-alumina.

The support may furthermore advantageously contain from 0.1 to 50% by weight of zeolite relative to the total weight of the support. In this case, any source of zeolite and any associated preparation method known to those skilled in the art may be incorporated. Preferably, the zeolite is selected from FAU, BEA, ISV, IWR, IWW, MEI, UWY, and preferably the zeolite is selected from FAU and BEA, such as Y and/or beta zeolite.

The support may also contain at least a portion of one or more group VIB and VIII metals, and/or at least a portion of one or more phosphorus-containing dopants, and/or at least a portion of one or more organic compounds containing oxygen (furan or other compounds) and/or nitrogen and/or sulfur, which are introduced independently of impregnation (e.g., during support preparation).

The carrier is advantageously in the form of beads, extrudates, pellets, or irregular and non-spherical agglomerates, the specific shape of which may depend on the crushing step.

The catalyst according to the invention also comprises furans. The furan compound can be a mono-furan or a multi-furan compound.

According to one variant, the furans have the formula (I)

Wherein the radicals R1, R2, R3 and R4 are each selected from the group consisting of hydrogen atoms, groups containing from 1 to 20 carbon atoms based on linear or branched or cyclic hydrocarbons, and functional groups selected from the group consisting of: aldehyde-C (O) H, ketone-C (O) R ₅ Carboxylic acid-COOH, ester-COOR ₆ hydroxymethyl-CH ₂ OH, alkoxymethyl-CH ₂ OR ₇ halomethyl-CH ₂ X wherein x=cl, br OR I, acyl halide-COX wherein x=cl, br OR I, alcohol-OH, ether OR ₈ mercaptomethyl-CH ₂ SH, (alkylthio) methyl-CH ₂ SR ₉ thioester-COSR ₁₀ Wherein R is ₅ To R ₁₀ Represents a group having from 1 to 20 carbon atoms based on a linear or branched or cyclic hydrocarbon, each of said groups R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 may further comprise heteroatoms, halogens and/or at least one functional group selected from: hydroxyl functionality, aldehyde functionality, ketone functionality, carboxyl functionality, alkanoate functionality, thiol functionality, alkylthio functionality, thioalkanoate functionality, and amine functionality.

In one variant, the radicals R3 and R4 each represent a hydrogen atom.

According to another variant, the furans are polyfurans having formula (II):

wherein Z is selected from oxygen atoms, sulfur atoms, groups based on linear or branched or cyclic hydrocarbons, said groups comprising from 1 to 20 carbon atoms, and which may further comprise heteroatoms, halogens and/or at least one functional group selected from: a hydroxyl function, an aldehyde function, a ketone function, a carboxyl function, an alkanoate function, a thiol function, an alkylthio function, a thioalkanoate function, and an amine function, and wherein the groups R1 and R2 are each selected from a hydrogen atom, a group containing 1 to 20 carbon atoms based on a linear or branched or cyclic hydrocarbon, a functional group selected from the group consisting of: aldehyde-C (O) H, ketone-C (O) R ₅ Carboxylic acid-COOH, ester-COOR ₆ hydroxymethyl-CH ₂ OH, alkoxymethyl-CH ₂ OR ₇ halomethyl-CH ₂ X wherein x=cl, br OR I, acyl halide-COX wherein x=cl, br OR I, alcohol-OH, ether OR ₈ mercaptomethyl-CH ₂ SH, (alkylthio) methyl-CH ₂ SR ₉ thioester-COSR ₁₀ Wherein R is ₅ To R ₁₀ Represents a group having from 1 to 20 carbon atoms based on a linear or branched or cyclic hydrocarbon, said groups R1, R2, R5, R6, R7, R8, R9 and R10 each may also comprise heteroatoms, halogens and/or at least one functional group chosen from: hydroxyl functionality, aldehyde functionality, ketone functionality, carboxyl functionality, alkanoate functionality, thiol functionality, alkylthio functionality, thioalkanoate functionality, and amine functionality.

The furans are preferably selected from the group consisting of 2-methylfuran (also known as Sylvan), 2, 5-dimethylfuran (also known as 2, 5-DMF), furfuryl alcohol (also known as furfuryl alcohol), 1- (2-furyl) ethanol, 2, 5-bis (hydroxymethyl) furan, 5- (hydroxymethyl) furfural (also known as 5- (hydroxymethyl) -2-furaldehyde or 5-HMF), 5-hydroxymethyl-2-furoic acid, 2-methoxyfuran, 2-furaldehyde (also known as furfural), 5-methyl-2-furaldehyde (also known as 5-methylfurfural), 5- (ethoxymethyl) furan-2-formaldehyde, 5-acetoxymethyl-2-furaldehyde 5-chloromethylfurfural, 2, 5-diformylfuran, 2-acetylfuran, 2-acetyl-5-methylfuran, furoic acid, 5-ethylfuroic acid, 5-formyl-2-furoic acid, 2, 5-furandicarboxylic acid, dimethyl 2, 5-furandicarboxylic acid, methyl 2-furoate, methyl 5-methyl-2-furoate, furylacetate, furfuryl propionate, furfurylthiol, 2- [ (methylsulfanyl) methyl ] furan, furfuryl thiocarboxylate, furfuryl thioacetate, furfuryl thiopropionate, methyl 2-thiofuroate, ethyl 3- (furfurfurylthio) propionate, furfuryl amine, 2-furoyl chloride.

When the furans are polyfurans of formula (II), they are preferably selected from the group consisting of bis (5-formylfurfuryl) ether, 2' - (thiodimethylene) difuran, and 5, 5-bis (5-methyl-2-furyl) -2-pentanone (also known as Sylvan trimer).

Preferably, the furans are selected from the group consisting of 2-furaldehyde (also known as furfural), 5-hydroxymethylfurfural (also known as 5- (hydroxymethyl) -2-furaldehyde or 5-HMF), 2-acetyl furan, 5-methyl-2-furaldehyde, methyl 2-furoate, furfuryl alcohol (also known as furfuryl alcohol) and furfuryl acetate.

The presence of furans in the catalyst makes it possible to observe an increased activity with respect to the known catalysts not impregnated with additives and the known dried additives impregnated with additives. The furans are present in the catalyst according to the invention in an amount of from 1% to 45% by weight, preferably from 2% to 30% by weight and more preferably from 3% to 25% by weight, relative to the total weight of the catalyst. During the preparation of the catalyst requiring a drying step, one or more drying steps, consecutive to the introduction of the furans, are carried out at a temperature lower than 200 ℃, so as to preferably retain the furans introduced in an amount of at least 30%, preferably at least 50%, and very preferably at least 70% calculated on the carbon remaining in the catalyst.

Furans may be derived from the conventional chemical industry with a generally high purity.

The furans may also originate from the processing of biomass, which will be referred to as bio-based (bio-based) furans, the products of this processing preferably contain predominantly furans, which may or may not be purified prior to use. Recent studies have shown the feasibility of producing furans from renewable resources such as sugar-producing biomass (e.g., starch, inulin, sucrose, cellulose, or hemicellulose) containing sugars (e.g., glucose and fructose) in the first or second generation. Examples which may be mentioned are the furfural production processes developed by Shell (WO 2012/04990), which may start with lignocellulosic biomass, to produce a mixture containing at least 50% by weight of furfural. Mention may also be made of the method of production of 5- (hydroxymethyl) furfural by hydrothermal carbonization of lignocellulosic biomass developed by Ava Biochem (WO 2012/119875).

The catalyst according to the invention may comprise, in addition to the furans, another organic compound or group of organic compounds known as such as an additive. The function of this additive is to increase the catalytic activity relative to the catalyst without the additive. More particularly, the catalyst according to the invention may also comprise, in addition to the furans, one or more oxygen-based organic compounds and/or one or more nitrogen-based organic compounds and/or one or more sulfur-based organic compounds. Preferably, the catalyst according to the invention may further comprise one or more oxygen-based organic compounds and/or one or more nitrogen-based organic compounds in addition to the furans. Preferably, the organic compound contains at least two carbon atoms and at least one oxygen and/or nitrogen atom.

Typically, the organic compound is selected from compounds comprising one or more chemical functional groups selected from the group consisting of: carboxyl, alcohol, thiol, thioether, sulfone, sulfoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea, and amide functionalities. Preferably, the organic compound is selected from compounds comprising two alcohol functions and/or two carboxyl functions and/or two ester functions and/or at least one amide function.

The oxygen-based organic compound may be one or more compounds selected from the group consisting of compounds comprising one or more chemical functional groups selected from the group consisting of: carboxyl, alcohol, ether, aldehyde, ketone, ester, and carbonate functional groups. For example, the oxygen-based organic compound may be one or more selected from the group consisting of: ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (having a molecular weight of 200 to 1500 g/mol), propylene glycol, 2-butoxyethanol, 2- (2-butoxyethoxy) ethanol, 2- (2-methoxyethoxy) ethanol, triethylene glycol dimethyl ether, glycerol, acetophenone, 2, 4-pentanedione, pentanone, acetic acid, maleic acid, malic acid, malonic acid, oxalic acid, gluconic acid, tartaric acid, citric acid, gamma-ketovaleric acid, C1-C4 dialkyl succinate, methyl acetoacetate, ethyl acetoacetate, 2-methoxyethyl 3-oxobutyrate, 2-methacryloxyethyl 3-oxobutyrate, dibenzofuran, crown ether, phthalic acid, glucose, gamma valerolactone, 2-acetylbutyrolactone, and propylene carbonate.

The nitrogen-based organic compound may be one or more compounds selected from the group consisting of chemical functional groups comprising one or more functional groups selected from the group consisting of amine and nitrile functional groups. For example, the nitrogen-based organic compound may be one or more selected from the group consisting of: ethylenediamine, diethylenetriamine, hexamethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, acetonitrile, octylamine, guanidine or carbazole.

The organic compound containing oxygen and nitrogen may be one or more compounds selected from the group consisting of compounds comprising one or more functional groups selected from the group consisting of: carboxyl, alcohol, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, amide, urea, and oxime functional groups. For example, the organic compound containing oxygen and nitrogen may be one or more selected from the group consisting of: 1, 2-cyclohexanediamine tetraacetic acid, monoethanolamine (MEA), N-methylpyrrolidone, dimethylformamide, ethylenediamine tetraacetic acid (EDTA), alanine, glycine, nitrilotriacetic acid (NTA), N- (2-hydroxyethyl) ethylenediamine-N, N' -triacetic acid (HEDTA), diethylenetriamine pentaacetic acid (DPTA), tetramethylurea, glutamic acid, dimethylglyoxime, N-di (hydroxyethyl) glycine and tris (hydroxymethyl) methylglycine, or lactams.

The sulfur-based organic compound may be one or more compounds selected from the group consisting of compounds comprising one or more chemical functional groups selected from the group consisting of: thiol, thioether, sulfone, and sulfoxide functionalities. For example, the sulfur-based organic compound may be one or more selected from the group consisting of: thioglycolic acid, 2-hydroxy-4-methylthiobutanoic acid, sulfone derivatives of benzothiophene or sulfoxide derivatives of benzothiophene.

Preferably, the oxygen-based organic compound is preferably selected from: gamma valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene Diamine Tetraacetic Acid (EDTA), maleic acid, malonic acid, citric acid, gamma ketovaleric acid, dimethylformamide, N-methylpyrrolidone, propylene carbonate, 2-methoxyethyl 3-oxobutyrate, 2-methacryloyloxyethyl 3-oxobutyrate, N-di (hydroxyethyl) glycine and tris (hydroxymethyl) methylglycine.

When present, the content of the functionalized organic compound(s) impregnated with additives containing oxygen (in addition to furans) and/or nitrogen and/or sulfur in the catalyst according to the invention is from 1% to 30% by weight, preferably from 1.5% to 25% by weight and more preferably from 2% to 20% by weight, relative to the total weight of the catalyst.

Preparation method

The catalyst according to the invention may be prepared according to any method known to the person skilled in the art for preparing supported catalysts impregnated with additives with organic compounds.

According to a first variant, the catalyst according to the invention can be prepared by implementing a step of impregnation with a solution of said furanic compound, advantageously by a solvent containing a furanic compound diluted therein. According to this variant, the process for preparing the catalyst involves a step of adding the furans by liquid phase. After impregnation, a drying step is then necessary to remove the solvent and/or the amount of furans and thus to release the porosity required for the use of the catalyst.

According to the second and third variants, the catalyst according to the invention can be prepared by implementing a step of adding said furans by gas phase. These variants are described below.

Introduction of furans by liquid phase

According to a first variant, the catalyst according to the invention can be prepared according to a preparation method comprising the following steps:

a) Contacting a compound comprising a group VIB element, at least one compound comprising a group VIII element, a furanic compound and optionally phosphorus with an alumina or silica-alumina based support or contacting a regenerated catalyst comprising an alumina or silica-alumina based support, at least one group VIB element, at least one group VIII element and optionally phosphorus with a furanic compound to obtain a catalyst precursor,

b) Drying the catalyst precursor obtained in step a) at a temperature below 200 ℃ without subsequent calcination.

According to this modification, a method of preparing a fresh catalyst will be described first, and a method of preparing a regenerated catalyst will be described later.

I) Method for producing fresh catalyst

The contacting step a) comprises several embodiments, which differ significantly by the moment of introduction of the furanic compound, which can be carried out simultaneously with the impregnation of the metal (co-impregnation), or after the impregnation of the metal (post-impregnation), or before the impregnation of the metal (pre-impregnation). Furthermore, the contacting step may combine at least two embodiments, such as co-impregnation and post-impregnation. These various embodiments will be described below. Embodiments may be performed in one or more steps, alone or in combination.

It is important to note that the catalyst according to the invention does not undergo any calcination after the introduction of the furanic compound or any other organic compound containing oxygen and/or nitrogen and/or sulfur during its preparation process, so that the furanic compound or any other organic compound is at least partially retained in the catalyst. The term "calcination" herein means a heat treatment under a gas containing air or oxygen at a temperature greater than or equal to 200 ℃.

However, the catalyst precursor may be subjected to a calcination step prior to the introduction of the furanic compound or any other organic compound containing oxygen and/or nitrogen and/or sulfur, in particular after impregnation of the group VIB and group VIII elements (post impregnation), optionally in the presence of phosphorus and/or other dopants, or during the regeneration of the used catalyst. The hydrogenation function (also called active phase) of the catalyst according to the invention, comprising elements of group VIB and VIII, is then in the form of an oxide.

According to another variant, the catalyst precursor does not undergo any calcination step after impregnation of the elements of groups VIB and VIII (post impregnation), it is simply dried. The hydrogenation function (also called active phase) of the catalyst according to the invention, comprising elements of group VIB and VIII, is then not in the form of an oxide.

Regardless of the embodiment, the contacting step a) generally involves at least one impregnation step, preferably a dry impregnation step, wherein the support is impregnated with an impregnation solution comprising at least one group VIB element, at least one group VIII element and optionally phosphorus. In the case of co-impregnation, described in detail below, this impregnation solution also comprises at least one furanic compound. The group VIB and VIII elements are generally introduced by impregnation, preferably by dry impregnation, or by impregnation in an excess of solution. Preferably, whatever the embodiment, the total amount of group VIB and group VIII elements is introduced by impregnation, preferably by dry impregnation.

It is also possible to introduce the elements of groups VIB and VIII partly during the shaping of the support, while blending with at least one alumina gel chosen as matrix, and then to introduce the remaining hydrogenation elements by impregnation. Preferably, when the group VIB and group VIII elements are partly introduced at the time of blending, the proportion of group VIB elements introduced during this step is less than 5 wt.% of the total amount of group VIB elements introduced into the final catalyst.

Preferably, the group VIB element is introduced simultaneously with the group VIII element, regardless of the method of introduction.

Molybdenum precursors that can be used are those of skill in the artAs is well known. For example, in the source of molybdenum, oxides and hydroxides, molybdic acid and salts thereof, in particular ammonium salts such as ammonium molybdate, ammonium heptamolybdate, phosphomolybdic acid (H) ₃ PMo ₁₂ O ₄₀ ) And salts thereof, and optionally silicomolybdic acid (H) ₄ SiMo ₁₂ O ₄₀ ) And salts thereof. The source of molybdenum may also be, for example, keggin, lacunar Keggin, substituted Keggin, dawson, anderson or Strandberg-type heteropoly compounds. Molybdenum trioxide and Keggin, lacunar Keggin or substituted Keggin-type heteropolyanions are preferably used.

Tungsten precursors that may be used are also well known to those skilled in the art. For example, in the source of tungsten, oxides and hydroxides, tungstic acid, and salts thereof, particularly ammonium salts such as ammonium tungstate, ammonium metatungstate, phosphotungstic acid, and salts thereof, and optionally silicotungstic acid (H ₄ SiW ₁₂ O ₄₀ ) And salts thereof. The source of tungsten may also be, for example, keggin, lacunar Keggin, substituted Keggin, or a heteropoly compound of the Dawson type. Preference is given to using oxides and ammonium salts, for example ammonium metatungstate or Keggin, lacunar Keggin, or substituted heteropolyanions of the Keggin type.

The precursors of the elements of group VIII that can be used are advantageously chosen from oxides, hydroxides, hydroxycarbonates, carbonates and nitrates of the elements of group VIII. For example, basic nickel carbonate or cobalt hydroxide is preferably used.

When phosphorus is present, it may be introduced in whole or in part by impregnation. Preferably, it is introduced by impregnation, preferably dry impregnation, by means of a solution of a precursor containing elements of groups VIB and VIII.

The phosphorus may advantageously be introduced alone or as a mixture with at least one element of group VIB and group VIII, and if the hydrogenation function is introduced in several parts, the introduction may be done in any step of impregnation of the hydrogenation function. The phosphorus may also be introduced in whole or in part during impregnation of the furans, if the furans are introduced separately from the hydrogenation function (in the case of post-impregnation and pre-impregnation described later), and this may be done in the presence or absence of organic compounds other than furans containing oxygen and/or nitrogen and/or sulfur. It may also be introduced at any step in the synthesis of the vector during the synthesis thereof. It may be introduced before, during or after blending of the selected alumina gel matrix (e.g., and preferably alumina hydrate (aluminum oxyhydroxide) (boehmite), which is an alumina precursor).

Preferred phosphorus precursors are orthophosphoric acid H ₃ PO ₄ But salts and esters thereof, such as ammonium phosphate, are also suitable for use. Phosphorus may also be introduced simultaneously with one or more group VIB elements in the form of Keggin, lacunar Keggin, substituted Keggin or Strandberg heteropolyanions.

The furans are advantageously introduced in an impregnation solution, which, depending on the preparation method, may be the same solution as the solution containing the elements of groups VIB and VIII or a different solution, in a total amount corresponding to:

the molar ratio of furanic compound of the catalyst precursor to the element or elements of group VIB is from 0.01 to 5mol/mol, preferably from 0.05 to 3mol/mol, preferably from 0.1 to 1.5mol/mol, and very preferably from 0.2 to 1mol/mol, calculated on the basis of the components introduced into the impregnation solution or solutions, and

the molar ratio of furanic compound of the catalyst precursor to the one or more elements of group VIII is from 0.02 to 17mol/mol, preferably from 0.1 to 10mol/mol, preferably from 0.2 to 5mol/mol, and very preferably from 0.4 to 3.5mol/mol, calculated on the basis of the components introduced into the one or more impregnation solutions.

Any of the impregnating solutions described in the present invention may comprise any polar solvent known to those skilled in the art. The polar solvent used is advantageously selected from: methanol, ethanol, water, phenol and cyclohexanol, alone or as a mixture. The polar solvent may also be advantageously selected from: propylene carbonate, DMSO (dimethyl sulfoxide), N-methylpyrrolidone (NMP) and sulfolane, alone or as a mixture. Polar protic solvents are preferably used. A list of conventional polar solvents and their dielectric constants can be found in book "Solvents and Solvent Effects in Organic Chemistry" C.Reichardt, wiley-VCH, third edition, 2003, pages 472-474. Very preferably, the solvent used is water or ethanol, and particularly preferably, the solvent is water. In one possible embodiment, the impregnating solution may be free of solvents, particularly during the pre-impregnation or post-impregnation preparation.

When the catalyst further comprises a dopant selected from boron, fluorine or a mixture of boron and fluorine, the introduction of this or these dopants can be carried out in different steps of the preparation and in different ways, in the same manner as described above for the introduction of phosphorus.

When the dopant is one, it is advantageously introduced as a mixture with one or more precursors of elements of groups VIB and VIII, by dry impregnation of the support using a solution, preferably an aqueous solution, of one or more precursors containing a metal precursor, a phosphorus precursor and one or more dopants (and also containing furans in co-impregnation mode) onto the shaped support.

The boron precursor may be boric acid, orthoboric acid (H) ₃ BO ₃ ) Ammonium diborate or pentaborate, boron oxide or borates. The boron may be introduced, for example, by a solution of boric acid in a water/ethanol mixture or in a water/ethanolamine mixture. If boron is introduced, the boron precursor is preferably orthoboric acid.

Fluorine precursors that may be used are well known to those skilled in the art. For example, the fluoride anions may be introduced in the form of hydrofluoric acid or a salt thereof. These salts are formed from alkali metals, ammonium or organic compounds. In the latter case, these salts are advantageously formed in the reaction mixture by reaction between the organic compound and hydrofluoric acid. The fluorine may be introduced, for example, by impregnation with hydrofluoric acid or an aqueous solution of ammonium fluoride or ammonium difluoride.

When the catalyst further comprises a further additive (in addition to the furans) or group of additives selected from organic compounds containing oxygen and/or nitrogen and/or sulfur in addition to the furans, it may be introduced into the impregnation solution of step a).

The molar ratio of the one or more organic compounds containing oxygen and/or nitrogen and/or sulfur to the one or more group VIB elements on the catalyst is from 0.05 to 5mol/mol, preferably from 0.1 to 4mol/mol, preferably from 0.2 to 3mol/mol, calculated on the basis of the components introduced into the one or more impregnation solutions.

The molar ratio of the one or more organic compounds containing oxygen and/or nitrogen and/or sulfur to the furans is from 0.05 to 5mol/mol, preferably from 0.1 to 4mol/mol, preferably from 0.2 to 3mol/mol, calculated on the basis of the components introduced into the one or more impregnation solutions.

Advantageously, the impregnated support is cured after each impregnation step. Curing causes the impregnating solution to become uniformly dispersed in the carrier.

Any of the curing steps described in the present invention are advantageously carried out at atmospheric pressure, in a water saturated atmosphere, and at a temperature of 17 to 50 ℃ and preferably at room temperature. Generally, a maturation time of ten minutes to forty-eight hours, and preferably thirty minutes to five hours, is sufficient. Longer times are not precluded, but do not necessarily provide any improvement.

According to step b) of the preparation process of the invention, the optionally cured catalyst precursor obtained in step a) is subjected to a drying step at a temperature below 200 ℃ without a subsequent calcination step.

Any drying step after the introduction of the furans described in the present invention is carried out at a temperature of less than 200 ℃, preferably from 50 to 180 ℃, preferably from 70 to 150 ℃, and very preferably from 75 to 130 ℃.

The drying step is advantageously carried out by any technique known to the person skilled in the art. It is advantageously carried out at atmospheric or reduced pressure. Preferably, this step is carried out at atmospheric pressure. It is advantageously implemented in a cross bed (cross bed) using hot air or any other hot gas. Preferably, when the drying is carried out in a fixed bed, the gas used is air or an inert gas, such as argon or nitrogen. Very preferably, the drying is carried out in the presence of nitrogen and/or air in a cross-bed. Preferably, the drying step has a short duration of 5 minutes to 4 hours, preferably 30 minutes to 4 hours, and very preferably 1 hour to 3 hours. Drying is then carried out to preferably retain at least 30% of the furans introduced during the impregnation step, calculated on the carbon remaining in the catalyst; preferably, this amount is greater than 50% and even more preferably greater than 70%. When organic compounds other than furans containing oxygen and/or nitrogen and/or sulfur are present, a drying step is carried out so as to preferably retain at least 30%, preferably at least 50%, and very preferably at least 70% of the amount introduced, calculated on the carbon remaining in the catalyst.

At the end of the drying step b), a dried catalyst is obtained which has not undergone any subsequent calcination step.

Co-impregnation

According to a first embodiment of step a) of the process for preparing the (fresh) catalyst, the compound comprising elements of groups VIB and VIII, the furanic compound and optionally phosphorus are deposited on the support by one or more co-impregnation steps, i.e. the compound comprising elements of groups VIB and VIII, the furanic compound and optionally phosphorus are introduced into the support simultaneously ("co-impregnation"). According to a variant, step a) is the following step:

a') impregnating a support based on alumina or silica-alumina with at least one solution containing at least one compound containing an element of group VIB, at least one compound containing an element of group VIII, furans and optionally phosphorus, thus obtaining a catalyst precursor.

The co-impregnation step or steps are preferably carried out by dry impregnation or by impregnation in an excess of solution. When this first mode comprises the implementation of several co-impregnation steps, it is preferred to carry out an intermediate drying step after each co-impregnation step, said intermediate drying step being carried out at a temperature lower than 200 ℃, advantageously between 50 and 180 ℃, preferably between 70 and 150 ℃, very preferably between 75 and 130 ℃, and optionally observing a maturation period between impregnation and drying.

Very preferably, during the preparation by co-impregnation, the aqueous impregnation solution of the group VIB and group VIII elements, the furans, optionally phosphorus, optionally further dopants selected from boron and/or fluorine, and optionally organic compounds containing oxygen and/or nitrogen and/or sulfur other than furans is introduced in step a) entirely after formation of the support by dry impregnation of the support with the precursors containing the group VIB and group VIII elements, the furans, optionally phosphorus precursors, optionally dopants selected from boron and/or fluorine precursors and optionally organic compounds containing oxygen and/or nitrogen and/or sulfur other than furans.

Post-impregnation

According to a second embodiment of step a) of the process for preparing a (fresh) catalyst according to the invention, at least one furanic compound is contacted with a dried and optionally calcined impregnated support comprising at least one group VIB element, at least one group VIII element and optionally phosphorus, thereby obtaining a catalyst precursor, said support being based on alumina or silica-alumina.

The second embodiment is the "post-dip" preparation of furans. Post-impregnation is carried out by, for example, dry impregnation.

According to this second embodiment, the contacting step a) comprises the following successive steps, which will be described in detail below:

a1 Impregnating a support based on alumina or silica-alumina with at least one solution containing at least one compound comprising a group VIB element, at least one compound comprising a group VIII element and optionally phosphorus, to obtain an impregnated support,

a2 Drying the impregnated support obtained in step a 1) at a temperature below 200 ℃ to obtain a dried impregnated support, and optionally calcining the dried impregnated support to obtain a calcined impregnated support,

a3 Impregnating the dried and optionally calcined impregnated support obtained in step a 2) with an impregnation solution comprising at least a furanic compound to obtain a catalyst precursor,

a4 Optionally curing the catalyst precursor obtained in step a 3).

In the implementation of step a 1) of the post impregnation, the introduction of the group VIB and group VIII elements and optionally phosphorus into the support may advantageously be carried out by one or more impregnations with an excess of solution on the support, or preferably by one or more dry impregnations, and preferably by only one dry impregnation of the support using one or more solutions, preferably one or more aqueous solutions, containing one or more metal precursors and preferably phosphorus precursors.

When several impregnation steps are carried out, an intermediate drying step is carried out, preferably at a temperature below 200 ℃, advantageously between 50 and 180 ℃, preferably between 70 and 150 ℃, very preferably between 75 and 130 ℃, after each impregnation step, and optionally a curing period is observed between impregnation and drying. After each intermediate drying step prior to the introduction of the furanic compound, there may be a calcination step under the conditions of step a 2) described below.

Very preferably, during the preparation by post-impregnation, an impregnation aqueous solution of the group VIB and group VIII elements and optionally phosphorus, optionally further dopants selected from boron and/or fluorine and optionally organic compounds containing oxygen and/or nitrogen and/or sulfur other than furans is introduced in step a 1) after forming the support by dry impregnation of the support with a precursor containing the group VIB and group VIII elements, a phosphorus precursor and optionally a dopant precursor selected from boron and/or fluorine and optionally an organic compound containing oxygen and/or nitrogen and/or sulfur other than furans.

According to another variant, the elements of groups VIB and VIII and optionally phosphorus, optionally further dopants selected from boron and/or fluorine and optionally organic compounds containing oxygen and/or nitrogen and/or sulfur, in addition to furans, can be introduced successively in step a 1) through several impregnation solutions containing one or more components.

Advantageously, the impregnated support obtained in step a 1) is cured under the conditions described for the curing above.

In step a 2), the impregnated support obtained in step a 1) is dried at a temperature below 200 ℃ to obtain an impregnated support dried under the conditions described for the drying above.

Optionally, the dried impregnated support may then be subjected to calcination. Calcination is generally carried out at a temperature of from 200 ℃ to 900 ℃, preferably from 250 ℃ to 750 ℃. Calcination time is usually 30 minutes to 16 hours, preferably 1 hour to 5 hours. Which is typically carried out in air. Calcination allows the precursors of the group VIB and group VIII metals to be converted to oxides.

In step a 3), the dried impregnated support obtained in step a 2) is impregnated with an impregnation solution comprising at least a furanic compound, thereby obtaining a catalyst precursor.

The furans may advantageously be deposited in one or more steps by overdose, or by dry impregnation, or by any other means known to those skilled in the art. Preferably, the furans are introduced by dry impregnation in the presence or absence of the solvents described above.

Preferably, the solvent in the impregnation solution used in step a 3) is water, which facilitates implementation on an industrial scale.

The furanic compound is advantageously introduced into the impregnation solution of step a 3) in the molar ratio per group VIB or group VIII element described above.

When it is also desired to introduce further additives (other than furans) or further additive groups selected from organic compounds containing oxygen and/or nitrogen and/or sulfur, said further additives may be introduced into the impregnation solution of step a 1) and/or into the impregnation solution of step a 3) or through a further impregnation step at any point in the preparation process prior to the final drying of step b), it is to be understood that no calcination step is carried out after its introduction. This compound is introduced in the proportions described above.

In step a 4), the catalyst precursor obtained in step a 3) is optionally cured, which is carried out under the curing conditions described above.

Step b) of the preparation process according to the invention, the catalyst precursor, which has optionally been cured in step a 4), is subjected to a drying step at a temperature below 200 ℃ without a subsequent calcination step, as described above.

Pre-impregnation

According to a third embodiment of step a) of the (fresh) catalyst preparation process of the present invention, at least one compound comprising a group VIB element, at least one compound comprising a group VIII element and optionally phosphorus are contacted with an alumina or silica-alumina based support containing furanic compounds to obtain a catalyst precursor.

This third embodiment is a "pre-impregnated" preparation of furans. This prepreg is carried out, for example, by dry impregnation.

According to this third embodiment, the contacting step a) comprises the following successive steps, which will be described in detail below:

a1') preparing a support comprising at least one furanic compound and optionally at least a portion of phosphorus,

a2 ') impregnating the support obtained in step a 1') with an impregnation solution comprising at least one compound comprising a group VIB element, at least one compound comprising a group VIII element and optionally phosphorus, thereby obtaining a catalyst precursor,

a3 ') optionally curing the catalyst precursor obtained in step a 2').

In a step a 1') carried out by means of prepressing, a support is prepared which comprises at least one furanic compound and optionally at least a portion of phosphorus. The furans may be introduced at any time during the preparation of the support, and are preferably introduced during the shaping or by impregnation onto the already shaped support.

If the introduction of the furans is chosen on a preformed support, this introduction can be carried out according to the post-impregnation step a 3). The optional curing step and drying at a temperature below 200 ℃ is then carried out under the curing and drying conditions described above.

If selected to be introduced during the shaping, the shaping is preferably carried out by extrusion blending, by granulation, by drop-on-solidification (oil-drop) method, by rotary disk granulation or via any other method known to the person skilled in the art. Very preferably, the shaping is carried out by extrusion blending, the furans being able to be introduced at any time of the extrusion blending. The shaped material obtained at the end of the shaping step is then advantageously subjected to a heat treatment step at a temperature such that at least a portion of the furanic compound is still present, preferably at a temperature lower than 200 ℃.

The same is true for the phosphorus optionally present in the support from step a 1'). The phosphorus may be introduced at any time during the preparation of the support and is preferably impregnated during the shaping or by impregnation onto the already shaped support as described above. If phosphorus is introduced solely during the shaping, i.e. without furanic compounds, said phosphorus is introduced by impregnation, the calcination temperature after its introduction can then advantageously be carried out at a temperature below 1000 ℃.

In the implementation of step a 2') of the post impregnation, the introduction of the group VIB and group VIII elements and optionally phosphorus may advantageously be carried out by one or more impregnations with an excess of solution on the support, or preferably by one or more dry impregnations, and preferably by only one dry impregnation of the support, using one or more solutions, preferably one or more aqueous solutions, containing one or more metal precursors and optionally phosphorus precursors.

Advantageously, the catalyst precursor obtained in step a 2') is cured under the curing conditions described above.

When it is also desired to introduce further additives (other than furans) or further additive groups selected from organic compounds containing oxygen and/or nitrogen and/or sulfur, said further additives may be introduced into the support of step a1 ') during shaping or by impregnation and/or into the impregnation solution of step a 2'), or by a further impregnation step at any point in the preparation process prior to the final drying of step b), it is to be understood that this introduction is not followed by any calcination step.

The three modes described above may be implemented as described alone or in combination to produce other hybrid preparation modes according to technical and practical constraints.

According to another alternative embodiment, the contacting step a) combines at least two modes of contact, for example co-impregnation of the organic compounds and post-impregnation of the organic compounds, which may be the same or different from the organic compounds used for co-impregnation, provided that at least one of the organic compounds is a furanic compound.

According to this alternative embodiment, the contacting step a) comprises the following successive steps:

a1 '') contacting a solution containing at least one compound comprising a group VIB element, at least one compound comprising a group VIII element, at least one organic compound containing oxygen and/or nitrogen and/or sulfur and optionally phosphorus with a support based on alumina or silica-alumina by co-impregnation, thereby obtaining an impregnated support,

a2 '') drying the impregnated support obtained from step a1 '') at a temperature below 200 ℃ without subsequent calcination thereof to obtain a dried impregnated support,

a3 '') contacting the dried impregnated support obtained from step a2 '') with a solution of at least one organic compound containing oxygen and/or nitrogen and/or sulfur, identical or different from that used in step a1 ''), to obtain a catalyst precursor,

a4 '') optionally curing the catalyst precursor obtained in step a3 ''),

and at least one organic compound of step a1 ") or step a 3") is a furanic compound.

Needless to say, the operating conditions described above are available in the case of this last embodiment.

II) method for producing a reconstituted catalyst

The catalyst according to the invention may be a reconstituted catalyst. When the furans are introduced by the liquid phase and therefore by the impregnation step, this catalyst can be prepared according to a preparation method comprising the following steps:

a) Contacting a regenerated catalyst comprising a support based on alumina or silica-alumina, at least one group VIB element, at least one group VIII element and optionally phosphorus with a furan compound to obtain a catalyst precursor,

b) Drying the catalyst precursor from step a) at a temperature below 200 ℃ without subjecting it to subsequent calcination.

In step a), the regenerated catalyst is contacted with a furan compound, thereby obtaining a catalyst precursor. Regenerated catalysts are catalysts which have been used as catalysts in catalytic units and in particular in hydrotreating and/or hydrocracking and which have undergone at least one step of partial or complete removal of coke, for example by calcination (regeneration). Regeneration may be performed by any means known to those skilled in the art. Regeneration is typically carried out by calcination at temperatures of from 350 to 550 ℃, and typically from 400 to 520 ℃, or from 420 to 520 ℃, or from 450 to 520 ℃, temperatures below 500 ℃ being generally advantageous.

The regenerated catalyst comprises a support based on alumina or silica-alumina, at least one element of group VIB, at least one element of group VIII and optionally phosphorus, in the proportions indicated above, respectively. After regeneration, the hydrogenation function of the regenerated catalyst, which contains elements of groups VIB and VIII, is in the form of an oxide. As described above, it may also contain dopants other than phosphorus.

According to this embodiment, the contacting step a) comprises the following successive steps:

a1″) impregnating a regenerated catalyst comprising a support based on alumina or silica-alumina, at least one group VIB element, at least one group VIII element and optionally phosphorus with an impregnation solution comprising at least one furanic compound, thereby obtaining a catalyst precursor,

a2'' ') optionally curing the catalyst precursor obtained in step a1' '').

Preferably, the contacting step a) is carried out by impregnating the regenerated catalyst with an impregnation solution comprising at least one furanic compound, thereby obtaining a catalyst precursor.

The furans may advantageously be deposited in one or more steps by impregnation in excess, or by dry impregnation, or by any other means known to the person skilled in the art. Preferably, the furanic compound is introduced by dry impregnation, as described above, in the presence or absence of a solvent.

Preferably, the solvent in the impregnation solution used is water, which is advantageous for implementation on an industrial scale.

Advantageously, the furanic compound is introduced into the impregnation solution in the molar ratio per group VIB or group VIII element described above.

When it is also desired to introduce a further additive (other than furans) or a group of further additives selected from organic compounds containing oxygen and/or nitrogen and/or sulfur, said further additive may be introduced into the impregnation solution of step a1' ' ') or through a further impregnation step at any point of the preparation process prior to the final drying of step b), it is to be understood that no calcination step is carried out after its introduction. This compound is introduced in the proportions described above.

In step a2'' '), the catalyst precursor obtained in step a1' '') is optionally cured, which is done under curing conditions as described above.

Step b) of the preparation process according to the invention, the catalyst precursor optionally cured in step a2' ' ') is subjected to a drying step at a temperature below 200 ℃ without a subsequent calcination step, as described above.

Introduction of furans by gas phase

According to the second and third variants, the fresh catalyst according to the invention can be prepared by carrying out the step of addition of the furans via the gas phase, as described in the french patent applications filed under the national numbers 17/53.921 and 17/53.922. According to these variants, the process for preparing the catalyst does not involve the usual steps of impregnation of the furans. Therefore, there is no need to perform a drying step after the introduction of the furans.

According to a second variant, the process for preparing the catalyst according to the invention comprises the following steps:

i) Depositing a furanic compound on an alumina or silica-alumina based support by performing a step in which the support and furanic compound in liquid form are brought together simultaneously at a temperature below the boiling point of the furanic compound and under pressure and time conditions such that a portion of the furanic compound is transferred into the support in gaseous form, without any physical contact between the support and the furanic compound in liquid form,

ii) contacting at least one compound comprising a group VIB element, at least one compound comprising a group VIII element and optionally phosphorus with an alumina or silica-alumina based support,

iii) Drying the solid obtained at the end of step ii),

step i) is carried out before or after steps ii) and iii), or during step iii).

The second variant is characterized in that the addition of the furans to the support is carried out without physical contact with the furans in liquid form, i.e. without impregnating the support with liquid. The method is based on the principle that there is a vapor pressure of a furanic compound, which is generated by a liquid phase of the furanic compound at a given temperature and a given pressure. A portion of the molecules of the furans in liquid form are thus converted into gaseous form (vaporized) and subsequently transferred (in gaseous form) into the carrier. Step i) of bringing this together is carried out for a time sufficient to obtain the target content of furans in the carrier.

Typically, step i) is carried out at an absolute pressure of 0 to 1 MPa.

Preferably, the operating temperature of step i) is below 200 ℃, preferably between 10 ℃ and 150 ℃, more preferably between 25 ℃ and 120 ℃.

According to a third variant, the process for preparing the catalyst according to the invention comprises the following steps:

i') depositing the furanic compound on a support based on alumina or silica-alumina by carrying out a step in which the support is brought together with a porous solid containing the furanic compound in a closed or open chamber, this step being carried out under conditions of temperature, pressure and time such that a portion of the furanic compound is transferred from the porous solid to the support in the gaseous state,

ii) contacting at least one compound comprising a group VIB element, at least one compound comprising a group VIII element, and optionally phosphorus with an alumina or silica-alumina based support,

iii) Drying the solid obtained at the end of step ii),

step i') is carried out separately before or after steps ii) and iii).

According to this third variant, the addition of the furans comprises bringing together, in an open or closed chamber, a first batch of porous solid enriched in furans, on which said furans have been previously deposited in liquid form, and a support, a second batch of porous solid low in furans. The purpose of bringing the porous solids together is to enable gaseous transfer of a portion of the furans contained in the first batch of porous solids to the second batch of porous solids. According to the present invention, the term "low furans" is intended to include substantially the case where the second batch of porous solids is free of said furans.

The third variant is based on the principle that furans have a vapor pressure at a given temperature and a given pressure. Thus, a portion of the furanic molecules of the furanic-enriched batch of porous solids are converted to gaseous form (vaporized) and subsequently transferred (in gaseous form) to a support (solids with low furanic content). According to the present invention, the porous solid enriched in furans serves as a source of furans that are enriched in furans as a carrier (porous solid with low furans content).

The porous solid enriched in furans is advantageously a porous support, preferably a support based on alumina or silica-alumina, possibly containing a group VIB element, at least one group VIII element and optionally phosphorus.

The mass ratio of (first solid rich in furans)/(second solid with low content of support or furans) depends on the pore distribution of the solids and on the target amount of furans on the solids obtained from step a) by pooling together. This mass ratio is generally less than or equal to 10, preferably less than 2, and even more preferably 0.05 to 1, inclusive.

The step of bringing together the batch of porous solids is preferably carried out under controlled temperature and pressure conditions and such that the temperature is below the boiling point of the furans to be transferred in the gaseous state. Preferably, the operating temperature is below 150 ℃, and the absolute pressure is typically 0 to 1MPa, preferably 0 to 0.5MPa, and more preferably 0 to 0.2MPa. The step of bringing together can thus be carried out in an open or closed chamber, optionally with control of the composition of the gases present in said chamber.

When the step of bringing the porous solids together occurs in an open chamber, it will be ensured that entrainment of furans out of the chamber is limited as much as possible. Alternatively the step of bringing together the porous solids may be carried out in a closed chamber, for example in a container for storing or transporting the solids, which container is impermeable to gas exchange with the external environment.

The term "brought together" means that the solids are present in the chamber at the same time without the two batches of solids necessarily having any physical contact.

The term "furan-rich" means that the solid contains more than 50%, preferably at least 60%, preferably at least 80%, preferably at least 90%, and preferably 100% of the total amount of said furan compound used in step i). According to one embodiment, the porous solid enriched in furans contains 100% of the total amount used in step i), and the carrier (second solid with a low furans content) thus contains 0% of the total amount of furans.

Two variants (second and third variants) of the preparation of the (fresh) catalyst by gas phase can be carried out according to the two embodiments a) and B).

According to a first embodiment a), the porous support is subjected to a step of impregnation with a solution containing a compound containing a group VIB element, a compound containing a group VIII element and optionally phosphorus, thereby depositing the active metal phase (step ii). The support impregnated with the active metal phase is optionally subjected to a curing step and subsequently dried (step iii) in order to remove the solvent introduced in step ii). Treating a dried support comprising an active metal phase and optionally phosphorus in step i) or i') together with a furan compound or a porous solid comprising a furan compound in liquid form, thereby providing a catalyst impregnated with the additive using the furan compound.

According to another embodiment B) for preparing the catalyst according to the invention, a catalyst support is used which does not contain an active phase. The support is first subjected to a step of adding a furanic compound, thereby providing a catalyst support impregnated with an additive using an organic compound (step i) or i'), the support being sent to a step of impregnation of the active phase after an optional maturation stage (step ii). This step may comprise contacting the additive-impregnated support with a solution containing at least one compound comprising a group VIB element, at least one compound comprising a group VIII element, and optionally phosphorus. The additive-impregnated catalyst thus obtained is optionally cured and subsequently subjected to a drying step (step iii) with the aim of removing the solvent introduced during the impregnation step of the metal precursor of the active phase.

In both embodiments a) and B), the porous support may in particular already contain further organic compounds in addition to furans.

It should be noted that step ii) of depositing the active metal phase may use a solution containing at least one compound comprising a group VIB element, at least one compound comprising a group VIII element, and optionally phosphorus, and one or more additional organic compounds other than step i) or i').

According to the fourth and fifth variants, it is also possible to carry out the step of adding the furans by gas phase on the regenerated catalyst.

According to these fourth and fifth variants, the method for preparing the catalyst according to the invention comprises the following steps:

i ") depositing a furanic compound on a regenerated catalyst comprising an alumina or silica-alumina based support, at least one group VIB element, at least one group VIII element and optionally phosphorus by performing a step in which the regenerated catalyst and the furanic compound in liquid form are brought together simultaneously without any physical contact between the catalyst and the furanic compound in liquid form, or at a temperature below the boiling point of the furanic compound and under pressure and time conditions such that a portion of the furanic compound is transferred to the catalyst in gaseous form

i ' ' ') by performing the step of bringing together the catalyst and the porous solid containing the furanic compound in a closed or open chamber, on a regenerated catalyst containing an alumina, or silica-alumina based support, at least one group VIB element, at least one group VIII element, and optionally phosphorus, under temperature, pressure, and time conditions such that a portion of the furanic compound is transferred from the porous solid to the catalyst in a gaseous state.

The catalyst impregnated with fresh or reconstituted additives obtained by introducing furans in the vapor phase as described above may also be treated in one or more subsequent steps to incorporate one or more other additional organic compounds different from those used in steps i), i ' ') or i ' ' '). The incorporation of one or more other further different organic compounds may be carried out by gas phase addition or according to any other method known to the person skilled in the art, for example by impregnation with a solution containing the further organic compound.

Vulcanization

The catalyst obtained according to one of the modes of introduction described in the present invention is advantageously converted into a sulfided catalyst before the catalyst is used in the hydrotreating and/or hydrocracking reactions, thereby forming the active species thereof. This activation or vulcanization step is carried out by methods well known to the person skilled in the art and advantageously under a sulfur-reducing (sulfo-reducing) atmosphere in the presence of hydrogen and hydrogen sulfide.

At the end of step b) of the various modes of the preparation process according to the invention, the catalyst obtained is therefore advantageously subjected to a sulfidation step without an intermediate calcination step.

The dried catalyst is advantageously sulfided ex situ or in situ. Sulfiding agent is H for activation of hydrocarbon feedstock for sulfiding catalyst purposes ₂ S gas or any other sulfur-based compound. The sulfur-based compound is advantageously selected from alkyl disulfides, such as dimethyl disulfide (DMDS), alkyl sulfides, such as dimethyl sulfide, mercaptans, polysulfides, such as n-butyl mercaptan (or 1-butyl mercaptan), t-nonyl polysulfide type, or any other compound known to those skilled in the art for obtaining good sulfiding of a catalyst. Preferably, the catalyst is sulfided in situ in the presence of a sulfiding agent and a hydrocarbon-based feedstock. Very preferably, the catalyst is sulfided in situ in the presence of dimethyl disulfide and a hydrocarbon-based feedstock.

Hydrotreating and/or hydrocracking process

Finally, another subject of the invention is the use of the catalyst according to the invention or of the catalyst prepared according to the preparation process according to the invention in a hydrotreating and/or hydrocracking process of hydrocarbon-based fractions.

The catalyst according to the invention, which has been preferably subjected to a prior sulfiding step, is advantageously used in hydroprocessing and/or hydrocracking reactions of hydrocarbon-based feedstocks, such as petroleum fractions, fractions obtained from coal or hydrocarbons produced from natural gas, optionally as mixtures or from hydrocarbon-based fractions obtained from biomass, and more particularly in hydrogenation, hydrodenitrogenation, hydrodearomatic hydrocarbons, hydrodesulphurisation, hydrodeoxygenation, hydrodemetallation or hydroconversion reactions of hydrocarbon-based feedstocks.

In these applications, the catalyst according to the invention, which has preferably undergone a prior sulfiding step, has an improved activity with respect to the catalysts of the prior art. The catalyst can also be advantageously used for the pretreatment of catalytic cracking or hydrocracking feedstocks, or for the hydrodesulphurisation of residues or for the forced hydrodesulphurisation of gas oils (ULSD: ultra low sulphur diesel).

The feedstock used in the hydrotreating process is, for example, gasoline, gas oil, vacuum gas oil, atmospheric residuum, vacuum residuum, atmospheric distillate, vacuum distillate, heavy fuel oil, wax and paraffin, used oil, deasphalted residuum or crude oil, feedstock derived from thermal or catalytic conversion processes, lignocellulosic feedstock or more generally feedstock obtained from biomass, alone or as a mixture. The treated feedstocks, and in particular those mentioned above, generally contain heteroatoms such as sulfur, oxygen and nitrogen, and for heavy feedstocks they generally also contain metals.

The operating conditions used in the process involving hydrotreating the reaction of the hydrocarbon feedstock described above are typically the following: the temperature is advantageously from 180℃to 450℃and preferably from 250℃to 440℃and the pressure is advantageously from 0.5 to 30MPa and preferably from 1 to 18MPa, and the hourly space velocity is advantageously from 0.1 to 20h ^-1 And preferably 0.2 to 5h ^-1 And the hydrogen/raw material ratio expressed as the volume of hydrogen/volume of the liquid raw material measured at normal temperature and normal pressure is favorably 50l/l to 5000l/l, and preferably 80 to 2000l/l.

According to a first mode of use, the hydrotreating process according to the invention is a process for hydrotreating and in particular Hydrodesulphurisation (HDS) of a gas oil fraction, carried out in the presence of at least one catalyst according to the invention. The hydrotreating process according to the invention involves removing sulfur-based compounds present in the gas oil fraction, thereby meeting current environmental standards, i.e. allowable sulfur content of at most 10 ppm. It also reduces the aromatics and nitrogen content of the gas oil fraction to be hydrotreated.

The gas oil fraction to be hydrotreated according to the process of the invention contains from 0.02 to 5.0 wt% of sulphur. It advantageously results from straight-run distillation (or straight-run gas oil) from a coking unit, visbreaking unit, steam cracking unit, unit for hydrotreating and/or hydrocracking heavier feedstocks, and/or from a catalytic cracking unit (fluid catalytic cracking). The gas oil fraction preferably contains at least 90% of compounds having a boiling point of 250 ℃ to 400 ℃ at atmospheric pressure.

The method of hydrotreating the gas oil fraction according to the invention is carried out under the following operating conditions: a temperature of 200 to 400 ℃, preferably 300 to 380 ℃, a total pressure of 2MPa to 10MPa, and more preferably 3MPa to 8MPa, expressed as a hydrogen volume measured at normal temperature and normal pressure conditions per volume of liquid feedstock, a hydrogen volume per volume of liquid feedstock based on hydrocarbon feedstock ratio of 100 to 600 liters/liter, and more preferably 200 to 400 liters/liter, and a Hourly Space Velocity (HSV) of 1 to 10h ^-1 Preferably 2 to 8h ^-1 . HSV corresponds to the inverse of the contact time in hours and is defined by the ratio of the volumetric flow rate of the liquid feedstock based on hydrocarbons/the volume of catalyst loaded in the reaction unit in which the hydrotreatment process according to the invention is carried out. The reaction unit for carrying out the method for hydrotreating the gas oil fraction in accordance with the invention is preferably carried out in a fixed bed, moving bed, or ebullating bed, preferably in a fixed bed.

According to a second mode of use, said hydrotreating and/or hydrocracking process according to the invention is a hydrotreating (in particular hydrodesulphurisation, hydrodenitrogenation, hydrogenation of aromatic compounds) and/or hydrocracking process of a vacuum distillate fraction carried out in the presence of at least one catalyst according to the invention. The hydrotreating and/or hydrocracking process according to the invention, also referred to as hydrocracking pretreatment or hydrocracking process, involves the removal of sulfur-based, nitrogen-based compounds, or aromatic compounds present in the distillate fraction as the case may be in order to carry out pretreatment prior to conversion in a catalytic cracking or hydroconversion process, or hydrocracking of the distillate fraction, which may optionally have been pretreated beforehand, if desired.

A very wide variety of feedstocks can be processed by the vacuum distillate hydrotreating and/or hydrocracking processes described above. Typically they contain at least 20% by volume, and typically at least 80% by volume, of compounds having a boiling point above 340 ℃ at atmospheric pressure. The feedstock may be, for example, a vacuum distillate and units derived from the extraction of aromatics from a lubricating oil base stock, or a solvent dewaxed feedstock and/or deasphalted oil derived from a lubricating oil base stock, or the feedstock may be deasphalted oil or paraffin derived from a Fischer-Tropsch process, or any mixture of the previously mentioned feedstocks. Typically, the feedstock has a T5 boiling point at atmospheric pressure above 340 ℃, and more preferably also above 370 ℃ at atmospheric pressure, i.e. 95% of the compounds present in the feedstock have a boiling point above 340 ℃, and more preferably also above 370 ℃. The nitrogen content of the feedstock treated in the process according to the invention is generally greater than 200 ppm by weight, preferably 500 to 10000 ppm by weight. The sulfur content of the feedstock treated in the process according to the invention is generally from 0.01% to 5.0% by weight. The feedstock may optionally contain metals (e.g., nickel and vanadium). Asphaltene content is typically less than 3000 ppm by weight.

Typically in the presence of hydrogen at a temperature of above 200 ℃, typically 250 ℃ to 480 ℃, advantageously 320 ℃ to 450 ℃, preferably 330 ℃ to 435 ℃, a pressure of above 1MPa, typically 2 to 25MPa, preferably 3 to 20MPa, 0.1 to 20.0h ^-1 And preferably 0.1 to 6.0h ^-1 Preferably 0.2 to 3.0h ^-1 The hydrotreating and/or hydrocracking catalyst is contacted with the feed as described previously and the amount of hydrogen introduced is such that the volume ratio of hydrogen lift per liter of hydrocarbon expressed as volume of hydrogen per volume of liquid feed measured at normal temperature and pressure conditions is 80 to 5000l/l and typically 100 to 2000l/l. These operating conditions used in the process according to the invention generally allow to obtain a conversion per pass to a product having a boiling point at atmospheric pressure of less than 340 ℃, and better even at atmospheric pressure of less than 370 ℃, of more than 15%, and even more preferably of from 20% to 95%.

Vacuum distillate hydrotreating and/or hydrocracking processes using catalysts according to the present invention encompass pressure ranges and conversion ranges extending from mild hydrocracking to high pressure hydrocracking. The term "mild hydrocracking" refers to hydrocracking that produces a moderate conversion, typically less than 40%, and operates at low pressure, preferably 2MPa to 6 MPa.

The catalyst according to the invention may be used alone in one or more fixed bed catalytic beds, one or more reactors, in a "single step" hydrocracking scheme with or without liquid recycle of unconverted fractions, or in a "two step" hydrocracking scheme, optionally in combination with a hydrofinishing catalyst located upstream of the catalyst according to the invention.

According to a third mode of use, the hydrotreating and/or hydrocracking process according to the invention is advantageously carried out as a pretreatment in a fluid catalytic cracking (or FCC: fluid catalytic cracking) process. The operating conditions of the pretreatment in terms of temperature range, pressure, hydrogen recycle rate, and hourly space velocity are generally the same as those described above for the vacuum distillate hydrotreating and/or hydrocracking process. The FCC process may be carried out under suitable cracking conditions with the objective of producing a smaller molecular weight hydrocarbon-based product by conventional methods known to those skilled in the art. A brief description of catalytic cracking will be found, for example, in Ullmann's Encyclopedia of Industrial Chemistry, volume a18, 1991, pages 61 to 64.

According to a fourth mode of use, said hydrotreating and/or hydrocracking process according to the invention is a hydrotreating (in particular hydrodesulphurisation) process of a gasoline fraction in the presence of at least one catalyst according to the invention.

Unlike other hydrotreating processes, hydrotreating (particularly hydrodesulfurization) of gasoline must be able to address double contradictory constraints: ensures deep hydrodesulfurization of gasoline and limits hydrogenation of unsaturated compounds present, thereby limiting octane number loss.

The feedstock is typically a hydrocarbon fraction having a distillation range of 30 to 260 ℃. Preferably, this hydrocarbon fraction is a gasoline-type fraction. Very preferably, the gasoline fraction is an olefinic gasoline fraction from, for example, a catalytic cracking unit (fluid catalytic cracking).

The hydrotreating process comprises contacting a hydrocarbon fraction with a catalyst according to the invention and hydrogen under the following conditions: a total pressure of 1 to 3MPa, preferably 1.5 to 2.5MPa, at a temperature of 200 to 400 ℃, preferably 230 to 330 ℃, at a volume flow of the feedstock defined as relative to the volume of the catalyst of 1 to 10h ^-1 Preferably 2 to 6 hours ^-1 And a hydrogen/steam of 100 to 600Nl/l, preferably 200 to 400Nl/lOil raw material volume ratio.

The gasoline hydrotreating process may be carried out in one or more reactors in series, either of the fixed bed type or the ebullated bed type. If the process is carried out using at least two reactors in series, it is possible to provide for the removal of H from the effluent from the first hydrodesulphurisation reactor ₂ S and then treating the effluent in a second hydrodesulfurization reactor.

The following examples demonstrate the significant gains in activity of catalysts prepared according to the process of the present invention over catalysts of the prior art and illustrate the invention in detail without limiting its scope.

Examples

Example 1: preparation of CoMoP catalysts C1 and C2 on alumina in the absence of organic Compounds (not according to the invention)

Adding cobalt, molybdenum and phosphorus to an alumina support having a diameter of 230m ² The BET specific surface area per gram, the pore volume of 0.78ml/g as measured by mercury porosimetry, and the average pore diameter defined as 11.5nm of the volume median diameter as measured by mercury porosimetry, and which is in the form of "extrudates". An impregnating solution was prepared by dissolving molybdenum oxide (21.1 g) and cobalt hydroxide (5.04 g) in 11.8g of an 85 wt% aqueous phosphoric acid solution at 90 ℃. After dry impregnation, the extrudate was cured at room temperature in a water saturated atmosphere for 24 hours and then dried at 90 ℃ for 16 hours. The dried catalyst precursor thus obtained is denoted as C1. Calcination of catalyst precursor C1 at 450 ℃ for 2 hours produced calcined catalyst C2. The final metal composition of catalyst precursor C1 and catalyst C2, expressed as oxides and relative to the weight of the dried catalyst, is then as follows:

MoO ₃ =19.5±0.2 wt%, coo=3.8±0.1 wt% and P ₂ O ₅ = 6.7 ± 0.1 wt%。

Example 2: preparation of CoMoP catalysts C3 (not according to the invention) and C4 (according to the invention) by co-impregnation on alumina

Cobalt, molybdenum and phosphorus were added to the alumina support previously described in example 1 and in the form of "extrudates". An impregnating solution was prepared by dissolving molybdenum oxide (28.28 g) and cobalt hydroxide (6.57 g) in an 85% aqueous solution of 15.85g phosphoric acid and water at 90 ℃. After homogenization of the aforementioned mixture, 38g of citric acid were added before the volume of the solution was adjusted to the pore volume of the support by adding water. The (citric acid)/Mo molar ratio is equal to 1mol/mol, and the (citric acid)/Co molar ratio is equal to 2.7mol/mol. After dry impregnation, the extrudate was cured at room temperature in a water saturated atmosphere for 24 hours and then dried at 120 ℃ for 16 hours. The dried catalyst thus obtained, impregnated with additives with citric acid, is denoted C3. The final composition of catalyst C3, expressed as oxide and relative to the weight of the dried catalyst, is then as follows:

MoO ₃ =19.6±0.2 wt%, coo=3.7±0.1 wt% and P ₂ O ₅ = 6.7 ± 0.1 wt%。

Catalyst C4 according to the invention was prepared as follows. Cobalt, molybdenum and phosphorus were added to the alumina support described in example 1 and in the form of "extrudates". An impregnating solution was prepared by dissolving molybdenum oxide (39 g) and cobalt hydroxide (9.3 g) in an 85% aqueous solution of 21.9g phosphoric acid and water at 90 ℃. After homogenization of the aforementioned mixture, 5- (hydroxymethyl) furfural was added to the solution in a proportion of 0.8mol/mol molybdenum, i.e. 2.2mol/mol cobalt, to produce catalyst precursor C4. The volume of the solution was adjusted to the pore volume of the support by adding water prior to impregnation. After dry impregnation, the catalyst precursor extrudates were cured at room temperature in a water saturated atmosphere for 24 hours and subsequently dried at 120 ℃ for 16 hours. The final composition of catalyst C4, expressed as oxide and relative to the weight of the dried catalyst, is then as follows:

MoO ₃ =19.5±0.2 wt%, coo=3.5±0.1 wt% and P ₂ O ₅ = 6.8 ± 0.1 wt%。

Example 3: preparation of CoMoP catalyst C5 (according to the invention) by post-impregnation on alumina

18g of the catalyst precursor C1 previously described in example 1 and in the form of an "extrudate" were impregnated with an aqueous solution containing 2.5g of 5- (hydroxymethyl) furfural, and the volume of the aqueous solution was equal to the pore volume of the catalyst precursor C1. The amount used was such that the amount of 5- (hydroxymethyl) furfural was 0.8mol/mol molybdenum (corresponding to 2.2mol/mol cobalt). The extrudate was cured at room temperature in a water saturated atmosphere for 16 hours. The catalyst precursor C5 was then dried at 120 ℃ for 2 hours to produce catalyst C5. The final metal composition of catalyst C5 relative to the weight of the dried catalyst was as follows:

MoO ₃ =19.5±0.2 wt%, coo=3.8±0.1 wt% and P ₂ O ₅ = 6.7 ± 0.1 wt%。

Example 4: preparation of CoMoP catalyst C6 on alumina by gas phase introduction of organic Compounds after Metal impregnation (according to the invention)

2.75g of 2-acetylfuran contained in the crystallization dish was placed in a closed chamber. 12g of catalyst precursor C1 was introduced into the same closed chamber and placed on a stainless steel screen such that liquid 2-acetylfuran was not in physical contact with catalyst precursor C1. The closed chamber was placed in an oven at 120 ℃ for 2 hours. After the catalyst precursor C1 had been brought together with the 2-acetylfuran compound in liquid form, 13.4g of catalyst C6 was thus obtained. The amount of 2-acetylfuran thus transferred to the catalyst was such that the molar ratio of 2-acetylfuran/Mo was 0.8mol/mol molybdenum (corresponding to 2.2mol/mol cobalt). The final metal composition of catalyst C6 relative to the weight of the dried catalyst was as follows:

MoO ₃ =19.5±0.2 wt%, coo=3.8±0.1 wt% and P ₂ O ₅ = 6.7 ± 0.1 wt%。

Example 5: preparation of CoMoP catalyst C7 on alumina by gas phase introduction of organic Compounds after Metal impregnation (according to the invention)

2.75g of 5-methyl-2-furaldehyde contained in the crystallization dish was placed in a closed chamber. 12g of procatalyst C1 was introduced into the same closed chamber and placed on a stainless steel screen such that the liquid 5-methyl-2-furaldehyde was not in physical contact with procatalyst C1. The closed chamber was placed in an oven at 120 ℃ for 2 hours. After the catalyst precursor C1 has been brought together with the 5-methyl-2-furaldehyde compound in liquid formThus, 13.4g of catalyst C7 was obtained. Whereby the amount of 5-methyl-2-furaldehyde transferred to the catalyst was such that the molar ratio of 5-methyl-2-furaldehyde/Mo was 0.8mol/mol molybdenum (corresponding to 2.2mol/mol cobalt). The final metal composition of catalyst C7 relative to the weight of the dried catalyst was as follows: moO (MoO) ₃ =19.5±0.2 wt%, coo=3.8±0.1 wt% and P ₂ O ₅ = 6.7 ± 0.1 wt%。

Example 6: preparation of CoMoP catalyst C8 on alumina by gas phase introduction of organic Compounds after Metal impregnation (according to the invention)

3.15g of methyl 2-furoate contained in the crystallization dishes was placed in a closed chamber. 12g of catalyst precursor C1 was introduced into the same closed chamber and placed on a stainless steel screen such that liquid methyl 2-furoate was not in physical contact with catalyst precursor C1. The closed chamber was placed in an oven at 120 ℃ for 2 hours. After the catalyst precursor C1 had been brought together with the methyl-2-furoate compound in liquid form, 13.6g of catalyst C8 was thus obtained. Whereby the amount of methyl 2-furoate transferred to the catalyst was such that the molar ratio of methyl 2-furoate/Mo was 0.8mol/mol molybdenum (corresponding to 2.2mol/mol cobalt). The final metal composition of catalyst C8 relative to the weight of the dried catalyst was as follows: moO (MoO) ₃ =19.5±0.2 wt%, coo=3.8±0.1 wt% and P ₂ O ₅ = 6.7 ± 0.1 wt%。

Example 7: preparation of CoMoP catalyst C9 on alumina by gas phase introduction of organic Compounds after Metal impregnation (according to the invention)

2.4g of 2-furaldehyde contained in the crystallization dish was placed in a closed chamber. 12g of catalyst precursor C1 were introduced into the same closed chamber and placed on a stainless steel screen such that liquid 2-furaldehyde was not in physical contact with catalyst precursor C1. The closed chamber was placed in an oven at 120 ℃ for 2 hours. After the catalyst precursor C1 had been brought together with the 2-furaldehyde compound in liquid form, 13.2g of catalyst C9 were thus obtained. Whereby the amount of 2-furaldehyde transferred to the catalyst was such that the molar ratio of 2-furaldehyde/Mo was 0.8mol/mol molybdenum (corresponding to 2.2mol/mol cobalt). Catalyst C9 final metal relative to the weight of dry catalystThe composition is as follows: moO (MoO) ₃ =19.5±0.2 wt%, coo=3.8±0.1 wt% and P ₂ O ₅ = 6.7 ± 0.1 wt%。

Example 8: hydrodesulfurization (HDS) evaluation of catalysts C1, C2 and C3 (not according to the invention) and C4, C5, C6, C7, C8 and C9 (according to the invention) gas oils

Catalysts C1, C2 and C3 (not according to the invention) and C4, C5, C6, C7, C8 and C9 (according to the invention) were tested in the HDS of gas oils.

The gas oil raw material used is characterized in that: density at 15 ℃ = 0.8522g/cm ³ Sulfur content = 1.44 wt.%.

Simulated distillation

- IP: 155℃

- 10%: 247℃

- 50%: 315℃

- 90%: 392℃

- FP: 444℃

This test was performed in an isothermal, cross-fixed bed pilot reactor with fluid circulating from the bottom upwards.

The catalyst precursor was first sulfided in situ in the reactor under pressure at 350 ℃ with the aid of the tested gas oil to which 2 wt.% dimethyl disulfide was added.

Hydrodesulfurization tests were performed under the following operating conditions: the total pressure is 7MPa, and the catalyst volume is 30cm ³ The temperature is 330 to 360 ℃, the hydrogen flow is 24 l/h, and the raw material flow is 60 cm ³ /h。

The catalytic properties of the catalysts tested are given in table 1. They are expressed in degrees celsius relative to the (comparative) catalyst C2 chosen as reference: they correspond to the temperature difference to be applied to achieve 50ppm of sulfur in the effluent. Negative values indicate that the target sulfur content is reached at lower temperatures and thus there is an increase in activity. A positive value indicates that the target sulfur content is obtained at a higher temperature and thus there is a loss of activity.

Table 1 clearly shows the gain of the catalytic effect provided by the organic compounds according to the invention. In particular, catalysts C4, C5, C6, C7, C8 and C9 (according to the invention) have a higher activity than the activity obtained for all the other catalysts evaluated. Thus, regardless of the method of introduction of the furans: the furans provide a gain in catalytic activity, co-impregnated with the metal, introduced in solution after metal impregnation (post-impregnation) and introduced in the gas phase after metal impregnation.

Although the catalyst according to the invention has a lower proportion of organic compounds than catalyst C3, the advantages of the catalyst according to the invention are significant and therefore have a higher intrinsic efficiency than other compounds for which a greater proportion of compounds has to be introduced in order to observe a significant catalytic effect.

Table 1: equal volume relative activity of catalysts C1 and C3 (not according to the invention) and C4, C5, C6, C7, C8 and C9 (according to the invention) relative to catalyst C2 (not according to the invention) in the hydrodesulfurization of gas oils

Catalysts (comparative or according to the invention)	Organic compound used and molar ratio of compound/Mo	Method for introducing organic compounds	HDS Activity
				C1 (comparison)	Without any means for	N/A	Basic value +1.0deg.C
C2 (comparison)	Without any means for	N/A	Basic value
				C3 (comparison)	Citric acid-1.0 mol/mol Mo	Co-impregnation	Basic value-2.9 DEG C
C4 (according to the invention)	5- (hydroxymethyl) furfural-0.8 mol/mol Mo	Co-impregnation	Basic value-5.8 DEG C
				C5 (according to the invention)	5- (hydroxymethyl) furfural-0.8 mol/mol Mo	Post-impregnation	Basic value-5.9 DEG C
C6 (according to the invention)	2-Acetylfuran-0.8 mol/mol Mo	Metal impregnation followed by gas phase	Basic value of-7.0 DEG C
				C7 (according to the invention)	5-methyl-2-furaldehyde-0.8 mol/mol Mo	Metal impregnation followed by gas phase	Basic value-7.2 DEG C
C8 (according to the invention)	2-Furfural acid methyl ester-0.8 mol/mol Mo	Metal impregnation followed by gas phase	Basic value-4.6 DEG C
				C9 (according to the invention)	2-Furan-0.8 mol/mol Mo	Metal impregnation followed by gas phase	Basic value-5.3 DEG C

Claims

1. A catalyst comprising a support based on alumina or silica-alumina, at least one element of group VIII, at least one element of group VIB and a furanic compound,

wherein the furans have the structure of formula (I)

Wherein the radicals R ₁ 、R ₂ 、R ₃ And R is ₄ Each selected from a hydrogen atom, a group containing 1 to 20 carbon atoms based on a linear or branched or cyclic hydrocarbon, a functional group selected from the following: aldehyde-C (O) H, ketone-C (O) R ₅ Carboxylic acid-COOH, ester-COOR ₆ hydroxymethyl-CH ₂ OH, alkoxymethyl-CH ₂ OR ₇ halomethyl-CH ₂ X, wherein x=cl, br OR I, acyl halide-COX, wherein x=cl, br OR I, alcohol-OH, ether OR ₈ mercaptomethyl-CH ₂ SH, (alkylthio) methyl-CH ₂ SR ₉ thioester-COSR ₁₀ Wherein R is ₅ To R ₁₀ Represents a group having 1 to 20 carbon atoms based on a linear or branched or cyclic hydrocarbon, said group R ₁ 、R ₂ 、R ₃ 、R ₄ 、R ₅ 、R ₆ 、R ₇ 、R ₈ 、R ₉ And R is ₁₀ Each also respectivelyMay contain heteroatoms, halogens and/or at least one functional group selected from the group consisting of: hydroxyl functionality, aldehyde functionality, ketone functionality, carboxyl functionality, alkanoate functionality, thiol functionality, alkylthio functionality, thioalkanoate functionality, and amine functionality; or (b)

Wherein the furans are polyfurans of formula (II)

Wherein Z is selected from oxygen atoms, sulfur atoms, groups containing 1 to 20 carbon atoms based on linear or branched or cyclic hydrocarbons, and which may further contain heteroatoms, halogens and/or at least one functional group selected from the group consisting of: hydroxyl functionality, aldehyde functionality, ketone functionality, carboxyl functionality, alkanoate functionality, thiol functionality, alkylthio functionality, thioalkanoate functionality, and amine functionality,

and wherein the radicals R ₁ And R is ₂ Each selected from a hydrogen atom, a group containing 1 to 20 carbon atoms based on a linear or branched or cyclic hydrocarbon, a functional group selected from the following: aldehyde-C (O) H, ketone-C (O) R ₅ Carboxylic acid-COOH, ester-COOR ₆ hydroxymethyl-CH ₂ OH, alkoxymethyl-CH ₂ OR ₇ halomethyl-CH ₂ X, wherein x=cl, br OR I, acyl halide-COX, wherein x=cl, br OR I, alcohol-OH, ether OR ₈ mercaptomethyl-CH ₂ SH, (alkylthio) methyl-CH ₂ SR ₉ thioester-COSR ₁₀ Wherein R is ₅ To R ₁₀ Represents a group having 1 to 20 carbon atoms based on a linear or branched or cyclic hydrocarbon, said group R ₁ 、R ₂ 、R ₅ 、R ₆ 、R ₇ 、R ₈ 、R ₉ And R is ₁₀ Each may also contain heteroatoms, halogens and/or at least one functional group selected from the group consisting of: hydroxyl functionality, aldehyde functionality, ketone functionality, carboxyl functionality, alkanoate functionality, thiol functionality, alkylthio functionality, thioalkanoate functionality, and amine functionality.

2. The catalyst of claim 1 wherein the group R in formula (I) ₃ And R is ₄ Respectively represent a hydrogen atom.

3. The catalyst of any one of claims 1 to 2, wherein the furans are selected from the group consisting of 2-methylfuran, 2, 5-dimethylfuran, furfuryl alcohol, 1- (2-furyl) ethanol, 2, 5-bis (hydroxymethyl) furan, 5- (hydroxymethyl) furfural, 5-hydroxymethyl-2-furoic acid, 2-methoxyfuran, 2-furaldehyde, 5-methyl-2-furaldehyde, 5- (ethoxymethyl) furan-2-formaldehyde, 5-acetoxymethyl-2-furaldehyde, 5-chloromethylfurfural, 2, 5-diformylfuran, 2-acetylfuran, 2-acetyl-5-methylfuran, furoic acid, 5-ethylfuroic acid, 5-formyl-2-furoic acid, 2, 5-furandicarboxylic acid dimethyl ester, 2-furoic acid methyl ester, 5-methyl-2-furoic acid methyl ester, furyl acetate, furyl propionate, furfuryl, 2- [ (methylthio) methyl ] furan, thioformate, thiofurfuryl acetate, thiofurfuryl propionate, 3-thiofurfuryl propionate, and ethyl thiofurfuryl propionate.

4. The catalyst of claim 1, wherein the furans are selected from the group consisting of bis (5-formylfurfuryl) ether, 2' - (thiodimethylene) difuran, and 5, 5-bis (5-methyl-2-furyl) -2-pentanone.

5. The catalyst according to any one of claims 1 to 2, wherein the content of group VIB element expressed as group VIB metal oxide is 5 wt.% to 40 wt.% relative to the total weight of the catalyst and the content of group VIII element expressed as group VIII metal oxide is 1 wt.% to 10 wt.% relative to the total weight of the catalyst.

6. The catalyst according to any one of claims 1 to 2, wherein the molar ratio of group VIII element to group VIB element in the catalyst is from 0.1 to 0.8.

7. The catalyst of any one of claims 1 to 2, further comprising phosphorus as P ₂ O ₅ The phosphorus content represented is from 0.1% to 20% by weight relative to the total weight of the catalyst, and the molar ratio of phosphorus to group VIB element in the catalyst is greater than or equal to 0.05.

8. The catalyst according to any one of claims 1 to 2, wherein the furans are present in an amount of 1 to 45% by weight relative to the total weight of the catalyst.

9. The catalyst according to any one of claims 1 to 2, further comprising an organic compound containing oxygen and/or nitrogen and/or sulfur in addition to the furanic compound.

10. The catalyst of claim 9, wherein the organic compound is selected from compounds comprising one or more chemical functional groups selected from the group consisting of: carboxyl, alcohol, thiol, thioether, sulfone, sulfoxide, ether, aldehyde, ketone, ester, carbonate, amine, nitrile, imide, oxime, urea, and amide functionalities.

11. The catalyst of claim 10, wherein the organic compound other than the furans is selected from the group consisting of: gamma valerolactone, 2-acetylbutyrolactone, triethylene glycol, diethylene glycol, ethylene Diamine Tetraacetic Acid (EDTA), maleic acid, malonic acid, citric acid, gamma ketovaleric acid, dimethylformamide, N-methylpyrrolidone, propylene carbonate, 2-methoxyethyl 3-oxobutyrate, 2-methacryloyloxyethyl 3-oxobutyrate, N-di (hydroxyethyl) glycine, tris (hydroxymethyl) methylglycine or lactam.

12. The catalyst of any one of claims 1 to 2, which is at least partially sulfided.

13. A method of preparing a catalyst according to any one of claims 1 to 12, comprising the steps of:

a. Contacting a compound comprising a group VIB element, at least one compound comprising a group VIII element, a furanic compound and optionally phosphorus with an alumina or silica-alumina based support or contacting a regenerated catalyst comprising an alumina or silica-alumina based support, at least one group VIB element, at least one group VIII element and optionally phosphorus with a furanic compound to obtain a catalyst precursor,

b. drying the catalyst precursor obtained in step a) at a temperature below 200 ℃ without subsequent calcination.

14. A method of preparing a catalyst according to any one of claims 1 to 12, comprising the steps of:

i) Depositing a furanic compound on an alumina or silica-alumina based support by performing a step in which the support and the furanic compound in liquid form are brought together simultaneously, without any physical contact between the support and the furanic compound in liquid form, at a temperature below the boiling point of the furanic compound and under pressure and time conditions such that a portion of the furanic compound is transferred into the support in gaseous form,

iii) Drying the solid obtained at the end of step ii),

step i) is carried out before or after steps ii) and iii) or during step iii).

15. A method of preparing a catalyst according to any one of claims 1 to 12, comprising the steps of:

i') depositing a furanic compound on an alumina or silica alumina-based support by performing a step in which the support is brought together with a furanic compound-containing porous solid in a closed or open chamber, under temperature, pressure and time conditions such that a portion of the furanic compound is transferred from the porous solid to the support in the gaseous state,

iii) Drying the solid obtained at the end of step ii),

Step i') is carried out separately before or after steps ii) and iii).

16. A method of preparing a catalyst according to any one of claims 1 to 12, comprising the steps of:

i ") depositing a furanic compound on a regenerated catalyst comprising an alumina or silica-alumina based support, at least one group VIB element, at least one group VIII element and optionally phosphorus by performing a step in which the regenerated catalyst and furanic compound in liquid form are brought together simultaneously at a temperature below the boiling point of furanic compound and under pressure and time conditions such that a portion of the furanic compound is transferred to the catalyst in gaseous form, and the catalyst and furanic compound in liquid form are free of any physical contact therebetween, or i'") depositing furanic compound on a regenerated catalyst comprising an alumina or silica-alumina based support, at least one group VIB element, at least one group VIII element and optionally phosphorus by performing a step in which the catalyst is brought together with a porous solid comprising furanic compound in a closed or open chamber such that a portion of the furanic compound is transferred from the furanic compound to the porous solid in gaseous form.

17. Use of a catalyst according to any one of claims 1 to 12 in a process for the hydrotreatment and/or hydrocracking of a hydrocarbon-based fraction.